Insulative products having bio-based binders

ABSTRACT

Fibrous insulation products have an aqueous binder composition that includes a carbohydrate and a crosslinking agent. In exemplary embodiments, the carbohydrate-based binder composition may also include a catalyst, a coupling agent, a process aid, a crosslinking density enhancer, an extender, a moisture resistant agent, a dedusting oil, a colorant, a corrosion inhibitor, a surfactant, a pH adjuster, and combinations thereof. The carbohydrate may be natural in origin and derived from renewable resources. Additionally, the carbohydrate polymer may have a dextrose equivalent (DE) number from 2 to 20. In at least one exemplary embodiment, the carbohydrate is a water-soluble polysaccharide such as dextrin or maltodextrin and the crosslinking agent is citric acid. Advantageously, the carbohydrates have a low viscosity and cure at moderate temperatures. The environmentally friendly, formaldehyde-free binder may be used in the formation of insulation materials and non-woven chopped strand mats. A method of making fibrous insulation products is also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of U.S. patent applicationSer. No. 12/900,540, filed Oct. 8, 2010, which claims priority benefitsfrom U.S. Provisional Patent Application Ser. No. 61/250,187 entitled“Bio-Based Binders For Insulation And Non-Woven Mats” filed Oct. 9,2009, the entire contents of which are expressly incorporated herein byreference.

TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION

The present invention relates generally to fibrous insulation productsand non-woven mats, and more particularly, to fibrous insulationproducts that contain a bio-based binder that contains no addedformaldehyde and is environmentally friendly.

BACKGROUND OF THE INVENTION

Conventional fibers are useful in a variety of applications includingreinforcements, textiles, and acoustical and thermal insulationmaterials. Although mineral fibers (e.g., glass fibers) are typicallyused in insulation products and non-woven mats, depending on theparticular application, organic fibers such as polypropylene, polyester,and multi-component fibers may be used alone or in combination withmineral fibers in forming the insulation product or non-woven mat.

Fibrous insulation is typically manufactured by fiberizing a moltencomposition of polymer, glass, or other mineral and spinning fine fibersfrom a fiberizing apparatus, such as a rotating spinner. To form aninsulation product, fibers produced by the rotating spinner are drawndownwardly from the spinner towards a conveyor by a blower. As thefibers move downward, a binder material is sprayed onto the fibers andthe fibers are collected into a high loft, continuous blanket on theconveyor. The binder material gives the insulation product resiliencyfor recovery after packaging and provides stiffness and handleability sothat the insulation product can be handled and applied as needed in theinsulation cavities of buildings. The binder composition also providesprotection to the fibers from interfilament abrasion and promotescompatibility between the individual fibers.

The blanket containing the binder-coated fibers is then passed through acuring oven and the binder is cured to set the blanket to a desiredthickness. After the binder has cured, the fiber insulation may be cutinto lengths to form individual insulation products, and the insulationproducts may be packaged for shipping to customer locations. One typicalinsulation product produced is a flexible insulation batt or blanket,which is suitable for use as wall insulation in residential dwellings oras insulation in the attic and floor insulation cavities in buildings.Another common insulation product is air-blown or loose-fill insulation,which is suitable for use as sidewall and attic insulation inresidential and commercial buildings as well as in any hard-to-reachlocations. Loose-fill insulation is formed of small cubes that are cutfrom insulation blankets, compressed, and packaged in bags.

Non-woven mats may be formed by conventional wet-laid processes. Forexample, wet chopped fibers are dispersed in a water slurry thatcontains surfactants, viscosity modifiers, defoaming agents, and/orother chemical agents. The slurry containing the chopped fibers is thenagitated so that the fibers become dispersed throughout the slurry. Theslurry containing the fibers is deposited onto a moving screen where asubstantial portion of the water is removed to form a web. A binder isthen applied, and the resulting mat is dried to remove any remainingwater and cure the binder. The formed non-woven mat is an assembly ofdispersed, individual glass filaments. An air-laid process is similarexcept that glass fibers are dispersed in a stream of air rather than ina water slurry.

Various attempts have been made to reduce undesirable formaldehydeemissions from formaldehyde-based resins. For example, variousformaldehyde scavengers such as ammonia and urea have been added to theformaldehyde-based resin in an attempt to reduce formaldehyde emissionfrom the insulation product. Because of its low cost, urea is addeddirectly to the uncured resin system to act as a formaldehyde scavenger.The addition of urea to the resin system produces urea-extendedphenol-formaldehyde resole resins. These resole resins can be furthertreated or applied as a coating or binder and then cured. Unfortunately,the urea-extended resoles are unstable, and because of this instability,the urea-extended resoles must be prepared on site. In addition, thebinder inventory must be carefully monitored to avoid processingproblems caused by undesired crystalline precipitates of dimer speciesthat may form during storage Ammonia is not a particularly desirablealternative to urea as a formaldehyde scavenger because ammoniagenerates an unpleasant odor and may cause throat and nose irritation toworkers. Further, the use of a formaldehyde scavenger in general isundesirable due to its potential adverse affects to the properties ofthe insulation product, such as lower recovery and lower stiffness.

In addition, previous arts have focused on the use of polyacrylic acidwith a polyhydroxy crosslinking agent or carbohydrate-based chemistrythat is linked to the Maillard reaction. Polyacrylic acid binders,however, have several drawbacks. For example, polyacrylic acid bindersuse petroleum based materials and costs typically at least two timesthat of current phenolic binder systems. In addition, the high viscosityand different cure characteristics pose process difficulties. Also,Maillard reaction-based products have an undesirable dark brown colorafter curing. Further, the use of large amounts of ammonia needed tomake the binder presents a safety risk and possible emission problems.

In view of the existing problems with current binders, there remains aneed in the art for a binder system that is not petroleum dependent, hasno added formaldehyde, is bio-based and environmentally friendly, and iscost competitive.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a binder compositionfor use in the formation of fiberglass insulation and non-woven choppedstrand mats that includes at least one carbohydrate that is natural inorigin and at least one crosslinking agent. The carbohydrate andcrosslinking agent form a polyester thermoset resin. The carbohydratemay have a dextrose equivalent (DE) from 2 to 20. Additionally, thecarbohydrate may be a water-soluble polysaccharide selected from pectin,dextrin, maltodextrin, starch, modified starch, starch derivatives andcombinations thereof. The crosslinking agent may be selected frompolycarboxylic acids, salts of polycarboxylic acid, anhydrides,monomeric and polymeric polycarboxylic acid with anhydride, citric acid,salts of citric acid, adipic acid, salts of adipic acid, polyacrylicacid, salts of polyacrylic acid, polyacrylic acid based resins, andcombinations thereof. In one or more embodiments, the crosslinking agentmay be citric acid or any monomeric or polymeric polycarboxylic acid andtheir corresponding salts. In some exemplary embodiments, the bindercomposition may include a moisture resistant agent and a pH adjuster.The binder composition is free of added formaldehyde and isenvironmentally friendly.

It is another object of the present invention to provide a fibrousinsulation product that includes a plurality of randomly oriented fibersand a binder composition applied to at least a portion of the fibers andinterconnecting the fibers. The binder includes at least onecarbohydrate that is natural in origin and at least one crosslinkingagent. Typically the carbohydrate will have reactive hydroxyl groups andthe crosslinking agent will have reactive carboxyl groups. Thecarbohydrate may have a dextrose equivalent (DE) from 2 to 20. Inexemplary embodiments, the carbohydrate is a water-solublepolysaccharide selected from pectin, dextrin, maltodextrin, starch,modified starch, starch derivatives, and combinations thereof. Thebinder composition may also include one or more members selected from acatalyst, a coupling agent, a process aid, a crosslinking densityenhancer, an extender, a moisture resistant agent, a dedusting oil, acolorant, a corrosion inhibitor, a surfactant, and a pH adjuster. Theprocess aid agent includes a polyol such as glycerol, triethanolamine,polyethylene glycol, and pentaerythritol. In one or more embodiment, thecrosslinking agent may be citric acid or any monomeric or polymericpolycarboxylic acid and their corresponding salts. Additionally, in lowdensity products (e.g., residential insulation products), the binder hasa light (e.g., white or tan) color after it has been cured.

It is yet another object of the present invention to provide a non-wovenchopped strand mat formed of a plurality of randomly oriented glassfibers having a discrete length enmeshed in the form of a mat having afirst major surface and a second major surface and a binder compositionat least partially coating the first major surface of the mat. Thebinder includes (1) at least one carbohydrate that is natural in originand has a dextrose equivalent from 2 to 20 and (2) at least onecrosslinking agent. The binder composition may also include one or moremembers selected from a catalyst, a moisture resistant agent, and a pHadjuster. In at least one exemplary embodiment, the carbohydrate is awater-soluble polysaccharide selected from pectin, dextrin,maltodextrin, starch, modified starch, starch derivatives andcombinations thereof. In addition, the crosslinking agent may beselected from polycarboxylic acids, salts of polycarboxylic acid,anhydrides, monomeric and polymeric polycarboxylic acid with anhydride,citric acid, salts of citric acid, adipic acid, salts of adipic acid,polyacrylic acid, salts of polyacrylic acid, polyacrylic acid basedresins, amino alcohols, sodium metaborate, polyoxyalkyleneamines,polyamines, polyols, and combinations thereof. The binder has a lightcolor upon curing, is environmentally friendly, and is free of addedformaldehyde.

It is an advantage of the present invention that the carbohydrate isnatural in origin and derived from renewable resources.

It is yet another advantage of the present invention that maltodextrinis readily available and is low in cost.

It is a further advantage of the present invention that insulationproducts and non-woven mats utilizing the inventive binder compositioncan be manufactured using current manufacturing lines, to make a varietyof product shapes, densities and uses, thereby saving time and money.

It is another advantage of the present invention that the bindercomposition has no added formaldehyde.

It is also an advantage of the present invention that the final producthas a light color that allows the use of dyes, pigments, or othercolorants to yield a variety of colors for the insulation product.Additionally, when finishing the surface of a board product with paintor a veil of woven or non-woven fabric, it takes less paint or fabricweight to cover these lighter colored boards than prior boards.

It is a further advantage of the present invention that the bindercomposition has a reduction in particulate emission compared toconventional phenol/urea/formaldehyde binder compositions.

It is a feature of the present invention that the carbohydrate polymermay have a dextrose equivalent (DE) number from 2 to 20.

It is a feature of the present invention that the maltodextrin can forman aqueous mixture that can be applied by conventional binderapplicators, including spray applicators.

It is a further feature of the present invention that the binder can beacidic, neutral, or basic.

It is another feature of the present invention that the inventiveinsulation products and non-woven mats have no added formaldehyde.

It is a further advantage of the present invention that the bindercomposition produces fibrous products, especially in lighter densityproducts, that have a softer feel to the touch, which is advantageous tothe installer or user of these fibrous products.

It is also a feature of the invention that the inventive bindercomposition can be useful for composite reinforcements, such as choppedstrands, for use in thermoplastics, thermosets, and roofingapplications. In addition, the inventive binders may be used in bothsingle and multi-end rovings.

The foregoing and other objects, features, and advantages of theinvention will appear more fully hereinafter from a consideration of thedetailed description that follows. It is to be expressly understood,however, that the drawings are for illustrative purposes and are not tobe construed as defining the limits of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages of this invention will be apparent upon consideration ofthe following detailed disclosure of the invention, especially whentaken in conjunction with the accompanying drawings wherein:

FIG. 1 is a schematic illustration of the formation of a facedinsulation product with the inventive binder composition according toone exemplary embodiment;

FIG. 2 is a is an elevational view of a manufacturing line for producinga fiberglass insulation product with the inventive binder compositionwhere the insulation product does not contain a facing materialaccording to another exemplary embodiment of the present invention; and

FIG. 3 is a schematic illustration of a wet-laid processing line forforming a chopped strand mat utilizing the inventive binder compositionaccording a further exemplary embodiment of the present invention.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, the preferred methodsand materials are described herein. All references cited herein,including published or corresponding U.S. or foreign patentapplications, issued U.S. or foreign patents, and any other references,are each incorporated by reference in their entireties, including alldata, tables, figures, and text presented in the cited references.

In the drawings, the thickness of the lines, layers, and regions may beexaggerated for clarity. It will be understood that when an element suchas a layer, region, substrate, or panel is referred to as being “on”another element, it can be directly on the other element or interveningelements may also be present. Also, when an element is referred to asbeing “adjacent” to another element, the element may be directlyadjacent to the other element or intervening elements may be present.The terms “top”, “bottom”, “side”, and the like are used herein for thepurpose of explanation only. Like numbers found throughout the figuresdenote like elements. It is to be noted that the phrase “binder”,“bio-based binder”, “binder composition”, and “binder formulation” maybe used interchangeably herein.

Bio-Based Binder Compositions

The present invention relates to environmentally friendly, aqueouspolyester binder compositions that contain at least one bio-basedcomponent. In one exemplary embodiment, the bio-based component is acarbohydrate and the binder and includes a carbohydrate and acrosslinking agent. Typically the carbohydrate has reactive hydroxylgroups and the crosslinking agent has reactive carboxyl groups. In someexemplary embodiments, the carbohydrate-based binder composition alsoincludes a coupling agent, a process aid agent, an extender, a pHadjuster, a catalyst, a crosslinking density enhancer, a deodorant, anantioxidant, a dust suppressing agent, a biocide, a moisture resistantagent, or combinations thereof. The binder may be used in the formationof insulation materials and non-woven chopped strand mats. In addition,the binder is free of added formaldehyde. Further, the bindercomposition has a reduction in particulate emission compared toconventional phenol/urea/formaldehyde binder compositions. The inventivebinder may also be useful in forming particleboard, plywood, and/orhardboards.

In one or more exemplary embodiment, the binder includes at least onecarbohydrate that is natural in origin and derived from renewableresources. For instance, the carbohydrate may be derived from plantsources such as legumes, maize, corn, waxy corn, sugar cane, milo, whitemilo, potatoes, sweet potatoes, tapioca, rice, waxy rice, peas, sago,wheat, oat, barley, rye, amaranth, and/or cassava, as well as otherplants that have a high starch content. The carbohydrate polymer mayalso be derived from crude starch-containing products derived fromplants that contain residues of proteins, polypeptides, lipids, and lowmolecular weight carbohydrates. The carbohydrate may be selected frommonosaccharides (e.g., xylose, glucose, and fructose), disaccharides(e.g., sucrose, maltose, and lactose), oligosaccharides (e.g., glucosesyrup and fructose syrup), and polysaccharides and water-solublepolysaccharides (e.g., pectin, dextrin, maltodextrin, starch, modifiedstarch, and starch derivatives).

The carbohydrate polymer may have a number average molecular weight fromabout 1,000 to about 8,000. Additionally, the carbohydrate polymer mayhave a dextrose equivalent (DE) number from 2 to 20, from 7 to 11, orfrom 9 to 14. The carbohydrates beneficially have a low viscosity andcure at moderate temperatures (e.g., 80-250° C.) alone or withadditives. The low viscosity enables the carbohydrate to be utilized ina binder composition. In exemplary embodiments, the viscosity of thecarbohydrate may be lower than 500 cps at 50% concentration and between20 and 30° C. The use of a carbohydrate in the inventive bindercomposition is advantageous in that carbohydrates are readily availableor easily obtainable and are low in cost.

In at least one exemplary embodiment, the carbohydrate is awater-soluble polysaccharide such as dextrin or maltodextrin. Thecarbohydrate polymer may be present in the binder composition in anamount from about 40% to about 95% by weight of the total solids in thebinder composition, from about 50% to about 95% by weight of the totalsolids in the binder composition, from about 60% to about 90%, or fromabout 70% to about 85%. As used herein, % by weight indicates % byweight of the total solids in the binder composition.

In addition, the binder composition contains a crosslinking agent. Thecrosslinking agent may be any compound suitable for crosslinking thecarbohydrate. In exemplary embodiments, the crosslinking agent has anumber average molecular weight greater than 90, from about 90 to about10,000, or from about 190 to about 4,000. In some exemplary embodiments,the crosslinking agent has a number average molecular weight less thanabout 1000. Non-limiting examples of suitable crosslinking agentsinclude polycarboxylic acids (and salts thereof), anhydrides, monomericand polymeric polycarboxylic acid with anhydride (i.e., mixedanhydrides), citric acid (and salts thereof, such as ammonium citrate),1,2,3,4-butane tetracarboxylic acid, adipic acid (and salts thereof),polyacrylic acid (and salts thereof), and polyacrylic acid based resinssuch as QXRP 1734 and Acumer 9932, both commercially available from TheDow Chemical Company. In exemplary embodiments, the crosslinking agentmay be any monomeric or polymeric polycarboxylic acid, citric acid, andtheir corresponding salts. The crosslinking agent may be present in thebinder composition in an amount up to about 50% by weight of the bindercomposition. In exemplary embodiments, the crosslinking agent may bepresent in the binder composition in an amount from about 5.0% to about40% by weight of the total solids in the binder composition or fromabout 10% to about 30% by weight.

Optionally, the binder composition may include a catalyst to assist inthe crosslinking. The catalyst may include inorganic salts, Lewis acids(i.e., aluminum chloride or boron trifluoride), Bronsted acids (i.e.,sulfuric acid, p-toluenesulfonic acid and boric acid) organometalliccomplexes (i.e., lithium carboxylates, sodium carboxylates), and/orLewis bases (i.e., polyethyleneimine, diethylamine, or triethylamine).Additionally, the catalyst may include an alkali metal salt of aphosphorous-containing organic acid; in particular, alkali metal saltsof phosphorus acid, hypophosphorus acid, or polyphosphoric acids.Examples of such phosphorus catalysts include, but are not limited to,sodium hypophosphite, sodium phosphate, potassium phosphate, disodiumpyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate,sodium hexamethaphosphate, potassium phosphate, potassiumtripolyphosphate, sodium trimetaphosphate, sodium tetramethaphosphate,and mixtures thereof. In addition, the catalyst or cure accelerator maybe a fluoroborate compound such as fluoroboric acid, sodiumtetrafluoroborate, potassium tetrafluoroborate, calciumtetrafluoroborate, magnesium tetrafluoroborate, zinc tetrafluoroborate,ammonium tetrafluoroborate, and mixtures thereof. Further, the catalystmay be a mixture of phosphorus and fluoroborate compounds. Other sodiumsalts such as, sodium sulfate, sodium nitrate, sodium carbonate may alsoor alternatively be used as the catalyst/accelerator. The catalyst orcure accelerator may be present in the binder composition in an amountfrom about 0% to about 10% by weight of the total solids in the bindercomposition, or from about 1.0% to about 5.0% by weight, or from about3.0% to about 5.0% by weight.

The binder composition may optionally contain at least one couplingagent. In at least one exemplary embodiment, the coupling agent is asilane coupling agent. The coupling agent(s) may be present in thebinder composition in an amount from about 0.01% to about 5.0% by weightof the total solids in the binder composition, from about 0.01% to about2.5% by weight, or from about 0.1% to about 0.5% by weight.

Non-limiting examples of silane coupling agents that may be used in thebinder composition may be characterized by the functional groups alkyl,aryl, amino, epoxy, vinyl, methacryloxy, ureido, isocyanato, andmercapto. In exemplary embodiments, the silane coupling agent(s) includesilanes containing one or more nitrogen atoms that have one or morefunctional groups such as amine (primary, secondary, tertiary, andquaternary), amino, imino, amido, imido, ureido, or isocyanato.Specific, non-limiting examples of suitable silane coupling agentsinclude, but are not limited to, aminosilanes (e.g.,3-aminopropyl-triethoxysilane and 3-aminopropyl-trihydroxysilane), epoxytrialkoxysilanes (e.g., 3-glycidoxypropyltrimethoxysilane and3-glycidoxypropyltriethoxysilane), methacryl trialkoxysilanes (e.g.,3-methacryloxypropyltrimethoxysilane and3-methacryloxypropyltriethoxysilane), hydrocarbon trialkoxysilanes,amino trihydroxysilanes, epoxy trihydroxysilanes, methacryl trihydroxysilanes, and/or hydrocarbon trihydroxysilanes. In one or more exemplaryembodiment, the silane is an aminosilane, such asγ-aminopropyltriethoxysilane.

Further exemplary coupling agents (including silane coupling agents)suitable for use in the binder composition are set forth below:

-   -   Acryl: 3-acryloxypropyltrimethoxysilane;        3-acryloxypropyltriethoxysilane;        3-acryloxypropylmethyldimethoxysilane;        3-acryloxypropylmethyldiethoxysilane;        3-methacryloxypropyltrimethoxysilane;        3-methacryloxypropyltriethoxysilane    -   Amino: aminopropylmethyldimethoxysilane;        aminopropyltriethoxysilane; aminopropyltrimethoxysilane/EtOH;        aminopropyltrimethoxysilane;        N-(2-aminoethyl)-3-aminopropyltrimethoxysilane;        N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane;        (2-aminoethyl)-(2-aminoethyl) 3-aminopropyltrimethoxysilane;        N-phenylaminopropyltrimethoxysilane    -   Epoxy: 3-Glycidoxypropylmethyldiethoxysilane;        3-glycidoxypropylmethyldimethoxysilane;        3-glycidoxypropyltriethoxysilane;        2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane;        2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane;        2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;        2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane    -   Mercapto: 3-mercaptopropyltrimethoxysilane;        3-Mercaptopropyltriethoxysilane;        3-mercaptopropylmethyldimethoxysilane;        3-Mercaptopropylmethyldiethoxysilane    -   Sulfide: bis[3-(triethoxysilyl)propyl]-tetrasulfide;        bis[3-(triethoxysilyl)propyl]-disulfide    -   Vinyl: vinyltrimethoxysilane; vinyltriethoxysilane; vinyl        tris(2-methoxyethoxy)silane; vinyltrichlorosilane;        trimethylvinylsilane    -   Alkyl: methyltrimethoxysilane; methyltriethoxysilane;        dimethyldimethoxysilane; dimethyldiethoxysilane;        tetramethoxysilane; tetraethoxysilane; ethyltriethoxysilane;        n-propyltrimethoxysilane; n-propyltriethoxysilane;        isobutyltrimethoxysilane; hexyltrimethoxysilane;        hexyltriethoxysilane; octyltrimethoxysilane;        decyltrimethoxysilane; decyltriethoxysilane;        octyltriethoxysilane; tert-butyldimethylchlorosilane;        cyclohexylmethyldimethoxysilane; dicylohexyldimethoxysilane;        cyclohexylethyldimethoxysilane; t-butylmethyldimethoxysilane    -   Chloroalkyl: 3-chloropropyltriethoxysilane;        3-chloropropyltrimethoxysilane;        3-chloropropylmethyldimethoxysilane    -   Perfluoro: decafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane;        ((heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane    -   Phenyl: phenyltrimethoxysilane; phenyltriethoxysilane;        diphenyldiethoxysilane; diphenyldimethoxysilane;        diphenyldichlorosilane    -   Hydrolyzates of the silanes listed above    -   Zirconates: zirconium acetylacetonate; zirconium methacrylate    -   Titanates: tetra-methyl titanate; tetra-ethyl titanate;        tetra-n-propyl titanate; tetra-isopropyl titanate;        tetra-isobutyl titanate; tetra-sec-butyl titanate;        tetra-tert-butyl titanate; mono n-butyl, trimethyl titanate;        mono ethyl tricyclohexyl titanate; tetra-n-amyl titanate;        tetra-n-hexyl titanate; tetra-cyclopentyl titanate;        tetra-cyclohexyl titanate; tetra-n-decyl titanate; tetra        n-dodecyl titanate; tetra (2-ethyl hexyl) titanate; tetra        octylene glycol titanate ester; tetrapropylene glycol titanate        ester; tetra benzyl titanate; tetra-p-chloro benzyl titanate;        tetra 2-chloroethyl titanate; tetra 2-bromoethyl titanate; tetra        2-methoxyethyl titanate; tetra 2-ethoxyethyl titanate.

Especially suitable titanate ester stabilizers of the invention areproprietary titanate ester compositions manufactured under the tradename Tyzor® by DuPont de Nemours & Co., Inc. Non-limiting examplesinclude Tyzor® titanate esters sold in the 100% form rather than assolutions, e.g., in a lower aliphatic alcohol, such as Tyzor® TBT(tetrabutyl titanate), Tyzor® TPT (tetraisopropyl titanate), and Tyzor®OG (tetraoctylene glycol titanate ester).

In addition, the binder composition may include a process aid (e.g.,polyol) in addition to the carbohydrates described above. The processaid is not particularly limiting so long as the process aid functions tofacilitate the processing of the fibers formation and orientation. Theprocess aid can be used to improve binder application distributionuniformity, to reduce binder viscosity, to increase ramp height afterforming, to improve the vertical weight distribution uniformity, and/orto accelerate binder de-watering in both forming and oven curingprocess. The process aid may be present in the binder composition in anamount from about 0% to about 25.0% by weight, from about 1.0% to about20.0% by weight, or from about 5.0% to about 15.0% by weight.

Examples of processing aids include viscosity modifiers (e.g., glycerol,1,2,4-butanetriol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol,poly(ethylene glycol) and defoaming agents (e.g., emulsions and/ordispersions of mineral, paraffin, or vegetable oils, dispersions ofpolydimethylsiloxane (PDMS) fluids and silica which has beenhydrophobized with polydimethylsiloxane or other materials, andparticles made of amide waxes such as ethylenebis-stearamide (EBS) orhydrophobized silica). A further process aid that may be utilized in thebinder composition is a surfactant. One or more surfactant may beincluded in the binder composition to assist in binder atomization,wetting, and interfacial adhesion.

The surfactant is not particularly limited, and includes surfactantssuch as, but not limited to, ionic surfactants (e.g., sulfate,sulfonate, phosphate, and carboxylate); sulfates (e.g., alkyl sulfates,ammonium lauryl sulfate, sodium lauryl sulfate (SDS), alkyl ethersulfates, sodium laureth sulfate, and sodium myreth sulfate); amphotericsurfactants (e.g., alkylbetaines such as lauryl-betaine); sulfonates(e.g., dioctyl sodium sulfosuccinate, perfluorooctanesulfonate,perfluorobutanesulfonate, and alkyl benzene sulfonates); phosphates(e.g., alkyl aryl ether phosphate and alkyl ether phosphate);carboxylates (e.g., alkyl carboxylates, fatty acid salts (soaps), sodiumstearate, sodium lauroyl sarcosinate, carboxylate fluorosurfactants,perfluoronanoate, and perfluorooctanoate); cationic (alkylamine saltssuch as laurylamine acetate); pH dependent surfactants (primary,secondary or tertiary amines); permanently charged quaternary ammoniumcations (e.g., alkyltrimethylammonium salts, cetyl trimethylammoniumbromide, cetyl trimethylammonium chloride, cetylpyridinium chloride, andbenzethonium chloride); and zwitterionic surfactants, quaternaryammonium salts (e.g., lauryl trimethyl ammonium chloride and alkylbenzyl dimethylammonium chloride), and polyoxyethylenealkylamines.

Suitable nonionic surfactants that can be used in conjunction with thisinvention include polyethers (e.g., ethylene oxide and propylene oxidecondensates, which include straight and branched chain alkyl and alkarylpolyethylene glycol and polypropylene glycol ethers and thioethers);alkylphenoxypoly(ethyleneoxy)ethanols having alkyl groups containingfrom about 7 to about 18 carbon atoms and having from about 4 to about240 ethyleneoxy units (e.g., heptylphenoxypoly(ethyleneoxy) ethanols,and nonylphenoxypoly(ethyleneoxy) ethanols); polyoxyalkylene derivativesof hexitol including sorbitans, sorbides, mannitans, and mannides;partial long-chain fatty acids esters (e.g., polyoxyalkylene derivativesof sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate);condensates of ethylene oxide with a hydrophobic base, the base beingformed by condensing propylene oxide with propylene glycol; sulfurcontaining condensates (e.g., those condensates prepared by condensingethylene oxide with higher alkyl mercaptans, such as nonyl, dodecyl, ortetradecyl mercaptan, or with alkylthiophenols where the alkyl groupcontains from about 6 to about 15 carbon atoms); ethylene oxidederivatives of long-chain carboxylic acids (e.g., lauric, myristic,palmitic, and oleic acids, such as tall oil fatty acids); ethylene oxidederivatives of long-chain alcohols (e.g., octyl, decyl, lauryl, or cetylalcohols); and ethylene oxide/propylene oxide copolymers.

In at least one exemplary embodiment, the surfactants are SURFONYL® 420,SURFONYL® 440, and SURFONYL® 465, which are ethoxylated2,4,7,9-tetramethyl-5-decyn-4,7-diol surfactants (commercially availablefrom Air Products and Chemicals, Inc. (Allentown, Pa.)), Stanfax (asodium lauryl sulfate), Surfynol 465 (an ethoxylated 2,4,7,9-tetramethyl5 decyn-4,7-diol), Triton™ GR-PG70 (1,4-bis(2-ethylhexyl) sodiumsulfosuccinate), and Triton™ CF-10 (poly(oxy-1,2-ethanediyl),alpha-(phenylmethyl)-omega-(1,1,3,3-tetramethylbutyl)phenoxy). Thesurfactant may be present in the binder composition in an amount from0.0% to about 10% by weight of the total solids in the bindercomposition, from about 0.01% to about 10% by weight, or from about 0.2%to about 5.0% by weight.

The binder composition may optionally include a corrosion inhibitor toreduce or eliminate any potential corrosion to the process equipment.The corrosion inhibitor can be chosen from a variety of agents, such as,for example, hexamine, benzotriazole, phenylenediamine,dimethylethanolamine, polyaniline, sodium nitrite, benzotriazole,dimethylethanolamine, polyaniline, sodium nitrite, cinnamaldehyde,condensation products of aldehydes and amines (imines), chromates,nitrites, phosphates, hydrazine, ascorbic acid, tin oxalate, tinchloride, tin sulfate, thiourea, zinc oxide, and nitrile. Alternatively,the corrosion can be reduced or eliminated by process control abatement,such as process water neutralization, removal of corrosive ingredients,and process water treatment to minimize the corrosivity. The corrosioninhibitor may be present in the binder composition in an amount fromabout 0% to about 15.0% by weight, from about 1.0% to about 5.0% byweight, or from about 0.2% to about 1.0% by weight.

Also, the binder composition may also contain one or more biocide suchas 3-iodo-2propyl-n-butylcarbamate, carbamic acid, butyl-,3-iodo-2-propynyl ester (IPBC), 2-bromo-2-nitropropane-1,3-diol,magnesium nitrate, 5-chloro-2-methyl-4-isothiazolin-3-one, magnesiumchloride, sulfamic acid, N-bromo, sodium salt,diiodomethyl-p-tolysulfone, dibromoacetonitrile, and2,2-dibromo-3-nitrilopropionamide to reduce or eliminate mold and fungalgrowth on the fiberglass product. The biocide may be present in thebinder composition in an amount from about 0% to about 10.0% by weight,from about 0.05% to about 1.0% by weight, or from 0.1% to about 0.5% byweight.

Further, the binder composition may optionally include at least onecrosslinking density enhancer to improve the degree of crosslinking ofthe carbohydrate based polyester binder. Crosslinking densityenhancement can be achieved by increasing esterification between thehydroxyl and carboxylic acid groups and/or introducing free radicallinkages to improve the strength of the thermoset resin. Theesterification crosslinking density can be adjusted by changing theratio between hydroxyl and carboxylic acid and/or adding additionalesterification functional groups such as triethanolamine,diethanolamine, mono ethanolamine, 1-amino-2-propanol,1,1′-aminobis-2-propanol, 1,1,′1″nitrilotri-2-propanol,2-methylaminoethanol, 2-dimethylaminoethanol, 2-(2-aminoethoxy)ethanol,2{(2-aminoethyl)amino}ethanol, 2-diethylaminoethanol,2-butylaminoethanol, 2-dibutylaminoethanol, 2cyclohexylaminoethanol,2,2′-(methylamino)bis-ethanol, 2,2′-(butylamino)bis-ethanol,1-methylamino-2propanol, 1-dimethylamino-2-propanol,1-(2-aminoethylamino)-2-propanol, 1,1′-(methylimino)bis-2-propanol,3-amino-1-propanol, 3-dimethylamino-1propanol, 2-amino-1-butanol,1-ethylamino-2-butanol, 4-diethylamino-1-butanol,1-diethylamino-2-butanol, 3-amino-2,2-dimethyl-1-propanol,2,2-dimethyl-3-dimethylamino-1-propanol, 4-diethylamino-2-butyn-1-ol,5-diethylamino-3-pentyne-2-ol, bis (2-hydroxypropyl)amine, as well asother alkanolamines, their mixtures, and their polymers. Another methodto achieve crosslinking density enhancement is to use bothesterification and free radical reaction for the crosslinking reactions.Chemicals that can be used for both reactions include maleic anhydride,maleic acid, or itaconic acid. The crosslinking density enhancer may bepresent in the binder composition in an amount from about 0% to about25.0% by weight, from about 1.0.0% to about 20.0% by weight, or fromabout 5.0% to about 15.0% by weight.

The binder may also include organic and/or inorganic acids and bases inan amount sufficient to adjust the pH to a desired level. The pH may beadjusted depending on the intended application, or to facilitate thecompatibility of the ingredients of the binder composition. In exemplaryembodiments, the pH adjuster is utilized to adjust the pH of the bindercomposition to an acidic pH. Examples of suitable acidic pH adjustersinclude inorganic acids such as, but not limited to sulfuric acid,phosphoric acid and boric acid and also organic acids likep-toluenesulfonic acid, mono- or polycarboxylic acids, such as, but notlimited to, citric acid, acetic acid and anhydrides thereof, adipicacid, oxalic acid, and their corresponding salts. Also, inorganic saltsthat can be acid precursors. The acid adjusts the pH, and in someinstances, as discussed above, acts as a crosslinking agent. Optionally,organic and/or inorganic bases, such sodium hydroxide, ammoniumhydroxide, and diethylamine, and any kind of primary, secondary, ortertiary amine (including alkanol amine), can be used for pH adjustment.The pH of the binder composition, when in an acidic state, may rangefrom about 1 to about 6, and in some exemplary embodiments, from about 2to about 5, including all amounts and ranges in between. In at least oneexemplary embodiment, the pH of the binder composition is about 2.5. ThepH adjuster in an acidic binder composition may be present in the bindercomposition in an amount sufficient to obtain the desired pH.

The binder composition may also contain a moisture resistant agent, suchas a alum, aluminum sulfate, latex, a silicone emulsion, apoly(organosiloxane), a hydrophobic polymer emulsion (e.g., polyethyleneemulsion or polyester emulsion), and mixtures thereof. For clarity, apoly(organosiloxane) is a polymer of the form —(—R₁SiR₂—)_(n)— whereinat least one of R₁ and R₂ is an organic radical, including, e.g. alkylor alkenyl, phenyl, etc. In at least one exemplary embodiment, the latexsystem is an aqueous latex emulsion. The latex emulsion includes latexparticles that are typically produced by emulsion polymerization. Inaddition to the latex particles, the latex emulsion may include water, astabilizer such as ammonia, and a surfactant. The moisture resistantagent may be present in the binder composition in an amount from 0% toabout 20% by weight of the total solids in the binder composition, fromabout 5.0% to about 10% by weight, or from about 5.0% to about 7.0% byweight.

Additionally, the binder may contain a dust suppressing agent to reduceor eliminate the presence of inorganic and/or organic particles whichmay have adverse impact in the subsequent fabrication and installationof the insulation materials. The dust suppressing agent can be anyconventional mineral oil, mineral oil emulsion, natural or syntheticoil, bio-based oil, or lubricant, such as, but not limited to, siliconeand silicone emulsions, polyethylene glycol, as well as any petroleum ornon-petroleum oil with a high flash point to minimize the evaporation ofthe oil inside the oven.

In addition, the binder may optionally include at least one extender toimprove the binder's appearance and/or to lower the overallmanufacturing cost. The extender can be an inorganic filler, such as tinoxide or calcium carbonate or organic materials such as lignin, ligninsulfonate, or a protein-based biomass. In exemplary embodiments, theextender is a protein-containing biomass. Like the carbohydrate, theprotein-containing biomass is natural in origin and is derived fromrenewable resources. For instance, the protein may be derived from plantsources such as soy (e.g., a soy flour), peanuts, sunflowers, kidneybeans, walnuts, or from other plants that have a high protein content.Alternatively, the protein may come from animal sources such as, but notlimited to, eggs, blood, and animal tissue (e.g., beef, pork, orchicken, as well as fish). The protein-containing biomass may contain upto about 95% protein, and in exemplary embodiments, up to 90%, 75%, or50% protein. As used herein, the term “protein” may be defined as amacromolecule composed of one or more polypeptides and includes anycombination of polypeptides regardless its amino acid sequence. Inaddition, the term “protein” is intended to include all possiblestructures in which a protein can be obtained naturally or a proteinthat has been modified to improve its reactivity. It is to beappreciated that derivatives of natural proteins and synthetic proteinsare also included within the scope of the term “protein”. In one or moreexemplary embodiment, the protein-containing biomass is soy flour. Theextender may be present in the binder composition in an amount fromabout 0% to about 70.0% by weight of the total solids in the bindercomposition, from about 5.0% to about 50.0% by weight, or from about10.0% to about 40.0% by weight.

The binder may optionally contain conventional additives such as, butnot limited to dyes, pigments, fillers, colorants, UV stabilizers,thermal stabilizers, anti-foaming agents, anti-oxidants, emulsifiers,preservatives (e.g., sodium benzoate), corrosion inhibitors, andmixtures thereof. Other additives may be added to the binder compositionfor the improvement of process and product performance. Such additivesinclude lubricants, wetting agents, surfactants, antistatic agents,and/or water repellent agents. Additives may be present in the bindercomposition from trace amounts (such as <about 0.1% by weight the bindercomposition) up to about 10.0% by weight of the total solids in thebinder composition. In some exemplary embodiments, the additives arepresent in an amount from about 0.1% to about 5.0% by weight of thetotal solids in the binder composition, from about 1.0% to about 4.0% byweight, or from about 1.5% to about 3.0% by weight.

The binder further includes water to dissolve or disperse the activesolids for application onto the reinforcement fibers. Water may be addedin an amount sufficient to dilute the aqueous binder composition to aviscosity that is suitable for its application to the reinforcementfibers and to achieve a desired solids content on the fibers. Inparticular, the binder composition may contain water in an amount fromabout 50% to about 98.0% by weight of the total solids in the bindercomposition.

The binder composition may be made by dissolving or dispersing thecrosslinking agent in water to form a mixture. Next, the carbohydratemay be mixed with the crosslinking agent in the mixture to form thebinder composition. If desired, a cure accelerator (i.e., catalyst) maybe added to the binder composition. The binder composition may befurther diluted with water to obtain a desired amount of solids. Ifnecessary, the pH of the mixture may be adjusted to the desired pH levelwith organic and inorganic acids and bases.

In the broadest aspect of the invention, the carbohydrate-based bindercomposition is formed of a carbohydrate (e.g., maltodextrin) and acrosslinking agent (e.g., polyacrylic acid or citric acid). The range ofcomponents used in the inventive binder composition according toembodiments of the invention is set forth in Table 1.

TABLE 1 % By Weight Component of Total Solids Carbohydrate 60.0-95.0Crosslinking Agent  5.0-40.0

Aqueous binder compositions according to other exemplary embodiments ofthe present invention that include a process aid agent (e.g., glycerol)or low molecular weight carbohydrate are set forth in Table 2.

TABLE 2 % By Weight Component of Total Solids Carbohydrate 5.0-90.0Process Aid Agent 1.0-40.0 Crosslinking Agent 5.0-40.0

Aqueous binder compositions according to further exemplary embodimentsof the present invention that include a process aid agent and acatalyst/cure accelerator are set forth in Table 3.

TABLE 3 % By Weight Component of Total Solids Carbohydrate 5.0-90.0Process Aid Agent 1.0-40.0 Crosslinking Agent 5.0-40.0 Catalyst/Cure1.0-5.0  AcceleratorFibrous Products with Bio-Based Binders

In one exemplary embodiment, the binder composition is used to form afibrous product, typically an insulation product. Fibrous products aregenerally formed of matted inorganic fibers bonded together by a curedthermoset polymeric material. Examples of suitable inorganic fibersinclude glass fibers, wool glass fibers, and ceramic fibers. Optionally,other reinforcing fibers such as natural fibers and/or synthetic fiberssuch as polyester, polyethylene, polyethylene terephthalate,polypropylene, polyamide, aramid, and/or polyaramid fibers may bepresent in the insulation product in addition to the glass fibers. Theterm “natural fiber” as used in conjunction with the present inventionrefers to plant fibers extracted from any part of a plant, including,but not limited to, the stem, seeds, leaves, roots, or phloem. Examplesof natural fibers suitable for use as the reinforcing fiber materialinclude basalt, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen,kenaf, sisal, flax, henequen, and combinations thereof. Insulationproducts may be formed entirely of one type of fiber, or they may beformed of a combination of types of fibers. For example, the insulationproduct may be formed of combinations of various types of glass fibersor various combinations of different inorganic fibers and/or naturalfibers depending on the desired application for the insulation. Theembodiments described herein are with reference to insulation productsformed primarily of glass fibers.

The term “fibrous products” is general and encompasses a variety ofcompositions, articles of manufacture, and manufacturing processes.“Fibrous products” may be characterized and categorized by manydifferent properties; density for example, which may range broadly fromabout 0.2 pounds/cubic foot (“pcf”) to as high as about 10 pcf,depending on the product. Low density flexible insulation batts andblankets typically have densities between about 0.2 pcf and about 5 pcf,more commonly from about 0.3 to about 4 pcf. Fibrous products alsoinclude higher density products having densities from about 1 to about10 pcf, more typically from about 2 or 3 pcf to about 8 pcf, such asboards and panels or formed products. Higher density insulation productsmay be used in industrial and/or commercial applications, including butnot limited to metal building insulation, pipe or tank insulation,insulative ceiling and wall panels, duct boards and HVAC insulation,appliance and automotive insulation, etc.

Another property useful for categorization is the rigidity of theproduct. Residential insulation batts are typically quite flexible andthey can be compressed into rolls or batts while recovering their “loft”upon decompression. In contrast, other fibrous products, such as ceilingtiles, wall panels, foundation boards and certain pipe insulation tomention a few, are quite rigid and inflexible by design. These productswill flex very little and are unlikely to be adapted or conformed to aparticular space.

Shape is another important property. Some fibrous products are flexible,as noted and can be forced to assume conforming shapes, while other areformed and shaped for a specific purpose. In some embodiments, the shapeis substantially planar, as in duct boards, ceiling tiles and some wallinsulation. In other embodiments, the fibrous insulation product ismanufactured with a particular shape (e.g. cylindrical) suitable for aparticular size conduit, pipe or tank. In other cases, specific shapesand cutouts, often die-cut, are included in certain appliance insulationproducts, automotive insulation products and the like. Finally, othershapes may be created with nonwoven textile insulation products.

Other classifications of fibrous insulation products can include themethod of manufacture. The manufacture of glass fiber insulation may becarried out in a continuous process by rotary fiberization of moltenglass, immediately forming a fibrous glass pack on a moving conveyor,and curing the binder on the fibrous glass insulation batt to form aninsulation blanket as depicted in FIG. 1. Glass may be melted in a tank(not shown) and supplied to a fiber forming device such as a fiberizingspinner 15. The spinners 15 are rotated at high speeds. Centrifugalforce causes the molten glass to pass through holes in thecircumferential sidewalls of the fiberizing spinners 15 to form glassfibers. Glass fibers 30 of random lengths may be attenuated from thefiberizing spinners 15 and blown generally downwardly, that is,generally perpendicular to the plane of the spinners 15, by blowers 20positioned within a forming chamber 25. It is to be appreciated that theglass fibers 30 may be the same type of glass or they may be formed ofdifferent types of glass. It is also within the purview of the presentinvention that at least one of the fibers 30 formed from the fiberizingspinners 15 is a dual glass fiber where each individual fiber is formedof two different glass compositions.

The blowers 20 turn the fibers 30 downward to form a fibrous batt 40.The glass fibers 30 may have a diameter from about 2 to about 9 microns,or from about 3 to about 6 microns. The small diameter of the glassfibers 30 helps to give the final insulation product a soft feel andflexibility.

The glass fibers, while in transit in the forming chamber 25 and whilestill hot from the drawing operation, are sprayed with the inventiveaqueous binder composition by an annular spray ring 35 so as to resultin a distribution of the binder composition throughout the formedinsulation pack 40 of fibrous glass. Water may also be applied to theglass fibers 30 in the forming chamber 25, such as by spraying, prior tothe application of the aqueous binder composition to at least partiallycool the glass fibers 30. The binder may be present in an amount fromabout 1% to 30% by weight of the total fibrous product, more usuallyfrom about 2% to about 20% or from about 3% to about 14%. Binder contentof the fibrous products is typically measured by loss on ignition or“LOI” of the cured product.

The glass fibers 30 having the uncured resinous binder adhered theretomay be gathered and formed into an uncured insulation pack 40 on anendless forming conveyor 45 within the forming chamber 25 with the aidof a vacuum (not shown) drawn through the fibrous pack 40 from below theforming conveyor 45. The residual heat from the glass fibers 30 and theflow of air through the fibrous pack 40 during the forming operation aregenerally sufficient to volatilize a majority of the water from thebinder before the glass fibers 30 exit the forming chamber 25, therebyleaving the remaining components of the binder on the fibers 30 as aviscous or semi-viscous high-solids liquid.

The coated fibrous pack 40, which is in a compressed state due to theflow of air through the pack 40 in the forming chamber 25, is thentransferred out of the forming chamber 25 under exit roller 50 to atransfer zone 55 where the pack 40 vertically expands due to theresiliency of the glass fibers. The expanded insulation pack 40 is thenheated, such as by conveying the pack 40 through a curing oven 60 whereheated air is blown through the insulation pack 40 to evaporate anyremaining water in the binder, cure the binder, and rigidly bond thefibers together. Heated air is forced though a fan 75 through the loweroven conveyor 70, the insulation pack 40, the upper oven conveyor 65,and out of the curing oven 60 through an exhaust apparatus 80. The curedbinder imparts strength and resiliency to the insulation blanket 10. Itis to be appreciated that the drying and curing of the binder may becarried out in either one or two different steps. The two stage(two-step) process is commonly known as B-staging.

Also, in the curing oven 60, the insulation pack 40 may be compressed byupper and lower foraminous oven conveyors 65, 70 to form a fibrousinsulation blanket 10. It is to be appreciated that the insulationblanket 10 has an upper surface and a lower surface. In particular, theinsulation blanket 10 has two major surfaces, typically a top and bottomsurface, and two minor or side surfaces with fiber blanket 10 orientedso that the major surfaces have a substantially horizontal orientation.The upper and lower oven conveyors 65, 70 may be used to compress theinsulation pack 40 to give the insulation blanket 10 a predeterminedthickness. It is to be appreciated that although FIG. 1 depicts theconveyors 65, 70 as being in a substantially parallel orientation, theymay alternatively be positioned at an angle relative to each other (notillustrated).

The curing oven 60 may be operated at a temperature from about 100° C.to about 325° C., or from about 250° C. to about 300° C. The insulationpack 40 may remain within the oven for a period of time sufficient tocrosslink (cure) the binder and form the insulation blanket 10. Theinventive binder composition cures at a temperature that is lower thanthe curing temperature of conventional formaldehyde binders. This lowercuring temperature requires less energy to heat the insulation pack, andnon-woven chopped strand mat described in detail below, which results inlower manufacturing costs.

A facing material 93 may then be placed on the insulation blanket 10 toform a facing layer 95. Non-limiting examples of suitable facingmaterials 93 include Kraft paper, a foil-scrim-Kraft paper laminate,recycled paper, and calendared paper. The facing material 93 may beadhered to the surface of the insulation blanket 10 by a bonding agent(not shown) to form a faced insulation product 97. Suitable bondingagents include adhesives, polymeric resins, asphalt, and bituminousmaterials that can be coated or otherwise applied to the facing material93. The faced fibrous insulation 97 may subsequently be rolled forstorage and/or shipment or cut into predetermined lengths by a cuttingdevice (not illustrated). Such faced insulation products may be used,for example, as panels in basement finishing systems, as ductwrap,ductboard, as faced residential insulation, and as pipe insulation. Itis to be appreciated that, in some exemplary embodiments, the insulationblanket 10 that emerges from the oven 60 is rolled onto a take-up rollor cut into sections having a desired length and is not faced with afacing material 94. Optionally, the insulation blanket 10 may be slitinto layers and by a slitting device and then cut to a desired length(not illustrated).

A significant portion of the insulation placed in the insulationcavities of buildings is in the form of insulation blankets rolled frominsulation products such as is described above. Faced insulationproducts are installed with the facing placed flat on the edge of theinsulation cavity, typically on the interior side of the insulationcavity. Insulation products where the facing is a vapor retarder arecommonly used to insulate wall, floor, or ceiling cavities that separatea warm interior space from a cold exterior space. The vapor retarder isplaced on one side of the insulation product to retard or prohibit themovement of water vapor through the insulation product.

The presence of water, dust, and/or other microbial nutrients in theinsulation product 10 may support the growth and proliferation ofmicrobial organisms. Bacterial and/or mold growth in the insulationproduct may cause odor, discoloration, and deterioration of theinsulation product 10, such as, for example, deterioration of the vaporbarrier properties of the Kraft paper facing. To inhibit the growth ofunwanted microorganisms such as bacteria, fungi, and/or mold in theinsulation product 10, the insulation pack 40 may be treated with one ormore anti-microbial agents, fungicides, and/or biocides. Theanti-microbial agents, fungicides, and/or biocides may be added duringmanufacture or in a post manufacture process of the insulation product10. It is to be appreciated that the insulation product using theinventive binder composition can be a fiberglass batt as depicted, or asloosefill insulation, ductboard, ductliner, or pipe wrap (not depictedin the Figures).

Formed or shaped products may include a further step, optionally duringcure, that molds or shapes the product to its specific final shape.Rigid boards are a type of shaped product, the shape being planar. Othershaped products may be formed by dies or molds or other formingapparatus. Rigidity may be imparted by the use of higher density offibers and/or by higher levels of binder application. As an alternativeto rotary fiberizing, some fibrous insulation products, particularlyhigher density, non-woven insulation products, may be manufactured by anair-laid or wet-laid process using premade fibers of glass, otherminerals or polymers that are scattered into a random orientation andcontacted with binder to form the product.

In another embodiment of manufacture, the binder composition may be usedin combination with pre-manufactured fibers to form a non-woven choppedstrand mat. In particular, binder is added during the formation of thechopped strand mat in a wet-laid or air-laid mat processing line, wherethe fibers are dispersed by a water (or air) fluid. One exemplaryprocess of separately adding the coupling agent to the chopped strandmat is depicted in FIG. 3. It is to be appreciated that reference ismade herein to glass fibers, although the chopped strand mat could beformed of, or include, non-glass fibers. Chopped glass fibers 100 may beprovided to a conveying apparatus such as a conveyor 112 by a storagecontainer 114 for conveyance to a mixing tank 116 that contains varioussurfactants, viscosity modifiers, defoaming agents, and/or otherchemical agents with agitation to disperse the fibers and form a choppedglass fiber slurry (not shown). The glass fiber slurry may betransferred to a head box 118 where the slurry is deposited onto aconveying apparatus such as a moving screen or foraminous conveyor 120and a substantial portion of the water from the slurry is removed toform a web (mat) 122 of enmeshed fibers. The water may be removed fromthe web 122 by a conventional vacuum or air suction system (not shown).

The inventive binder 124 is applied to the web 122 by a suitable binderapplicator, such as the spray applicator 126 or a curtain coater (notillustrated). Once the binder 124 has been applied to the mat 122, thebinder coated mat 128 is passed through at least one drying oven 130 toremove any remaining water and cure the binder composition 124. Theformed non-woven chopped strand mat 132 that emerges from the oven 130is an assembly of randomly oriented, dispersed, individual glass fibers.The chopped strand mat 132 may be rolled onto a take-up roll 134 forstorage for later use as illustrated. The non-woven mat can be use inroofing, flooring, ceiling, wall applications, as filters, in groundbased vehicles, and in aircraft.

In some cases, it is even possible to use scraps of continuous fibers,such as E-glass, and cut them to lengths suitable for fluid-dispersedmanufacturing processes. In one embodiment of textile pipe insulation,lengths of scrap E-glass are cut ranging from about 0.5 to about 6inches, nominally about 2 inches in length. These are dispersed by afluid (water or air), the fluid is removed, and the fibers are sprayedwith a bio-based binder which is cured as before.

Some exemplary fibrous products that can be manufactured using thebio-based binders according to the invention include those illustratedin Table A below.

TABLE A Bio-based binder formulations for representative products*Flexible Metal Warm Duct Building & Dry Ceiling Tile boards MediaInsulation boards A B C Maltodextrin 65-70 65-70 65-70 65-70 45-50 55-60Citric Acid 25-30 25-30 25-30 25-30 30-35 25-30 Sodium 2-5 2-5 2-5 2-52-5 2-5 hypophosphite Glycerol 10-15 Polyglycol  7-10 Surfactant (e.g.0.1- 0.1- 0.1- 0.1- SURFYNOL 465) 0.3% 0.3% 0.3% 0.3% OrganopolysiloxaneUp to Up to 0.4- Up to Up to Up to moisture resistance 0.5% 0.5% 0.5%0.5% 0.5% 0.5% additive (e.g. Polon MR) *In Table A above, eachingredient of the binder composition is given as a range of typicalvalues of percentage of dry weight of the binder composition.

Whereas examples 4, 5, 7, and 12 relate to flexible, light densityresidential insulation, examples 8, 9 and 10 further illustratecommercial fibrous products other than the typical flexible residentialinsulation. A more complete listing of non-residential insulationfibrous products that can be manufactured using a bio-based bindercomposition according to the invention is set forth in Table B, below.

TABLE B Selected Commercial and Industrial Fibrous Products which mayuse a Bio-Based Binder Flexible, Light Density Rigid Pipe InsulationTextile E-glass Rigid Boards Insulation and pipe rolls Nonwoven DensityWide range of densities- Light density - Ranging Ranging from 3-6 pcfRanging from 0.8 to 4 pcf from 1.5 to 10 pcf from 0.3 to 4.0 pcf Bindercontent about 2 to about 20% LOI about 2 to about 13% LOI about 3 toabout 15% LOI about 5 to about 20% LOI Manufacturing Rotary fiberforming Rotary fiber forming Rotary fiber forming Air-laid nonwovenprocess method process process process plus on or offline molding/pipeformation process Exemplary QUIET R Duct Board Certified R MetalBuilding EVOLUTION Paper-Free QUIET R Textile Duct Owens Corning QUIET RDuct Liner Insulation ASJ Liner Products Board ELAMINATOR ®Pre-Engineered VAPORWICK Insulation DURAFLEX 700 Series Insulation MetalRoof Insulation FIBERGLAS ™ Pipe and Transportation Insul-QuickInsulation MBI Plus Tank Insulation rolls SCR Insulation Board MetalBldg Utility Blanket Curtainwall Unfaced Metal Building InsulationQuietZone Shaftwall for Canada Warm -N -Dri Flexible Duct MediaInsulation Energy Board QUIET R Rotary Duct Liner TremDrain SOFTR DuctWrap FRK Exterior Foundation TIW Types I and II Barrier Board FLEX-Wrapfor pipes and tanks Ceiling Board Blanks H2V Series RA Series SelectSound Thermorange FlameSpread 25 Sonobatts Thermal Batts

There are numerous advantages provided by the inventive binderformulations. For example, unlike conventional urea-formaldehydebinders, inventive binders have a light color after curing (in lowdensity products). In addition, the carbohydrate is natural in originand derived from renewable resources. By lowering or eliminatingformaldehyde emission, the overall volatile organic compounds (VOCs)emitted in the workplace are reduced. Additionally, becausecarbohydrates are relatively inexpensive, the insulation product orchopped fiber mat can be manufactured at a lower cost. Further, thebinder has low to no odor, making it more desirable to work with.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples illustrated belowwhich are provided for purposes of illustration only and are notintended to be all inclusive or limiting unless otherwise specified.

EXAMPLES Example 1

The binder formulations set forth in Table 4 were utilized to formhandsheets in the manner described in detail below. The nonwovenfiberglass handsheets were dried and cured for three minutes at 400° F.The tensile strength, the Loss on Ignition (LOI), and the tensilestrength divided by the LOI (tensile strength/LOI) for each sample wasdetermined under ambient and steam conditions. The tensile strength wasmeasured using Instron. The loss on ignition (LOI) of the reinforcingfibers is the reduction in weight experienced by the fibers afterheating them to a temperature sufficient to burn or pyrolyze the organicsize from the fibers. The loss on ignition was measured according to theprocedure set forth in TAPPI T-1013 OM06, Loss on Ignition of FiberglassMats (2006). To place the handsheet in a steam environment, thehandsheets were placed in an autoclave at 240° F. at a pressure between400 and 500 psi for 30 minutes.

The handsheets were made according to the following procedure. Firstwater is added to a bucket (approximately 5 liters). To this water, 8drops of NALCO dispersant 01NM 159 was added. A pneumatic stirrer waslowered into the bucket and set at a slow speed so as to stir but notproduce foam. To this stirring mixture, wet chop glass fibers (8 grams)were added and allowed to stir for 5 minutes. A screen catch was placedin a 12×12×12 inch 40 liter Williams standard pulp testing apparatus(a.k.a. a decide box) and the box was closed. The deckle box was thenfilled with water to the “3” mark and a plate stirrer was placed in thedeckle box. To the water in the decide box, a 0.5% wt. solution ofpolyacrylamide, NALCO 7768, (80 grams) was added and mixed untildissolved using the plate stirrer. After the glass fiber water hadstirred for 5 minutes, a 0.5% wt. solution of polyacrylamide, NALCO 7768(80 grams) was added and stirred at low speed for one minute, afterwhich the stirring speed was set to the highest setting and allowed tostir for an additional 2 minutes. The glass fiber solution is thenimmediately dumped into the deckle box and stirred with the platestirrer for 10 rapid strokes. At this point, the valve on the decide boxwas depressed until the deckle box was empty. After the decide box wasdrained, the box was opened and the screen with the handsheet wasremoved from the base by holding opposite corners of the screen. Thescreen was then placed on a wooden frame and the bio-based binder wasapplied to the handsheet using a roll coater. Excess binder was thenvacuumed off. The binder-coated handsheet was placed into an oven forcuring and cut into one inch strips. These strips were placed in adesiccator overnight.

The results of this experiment are set forth in Table 5. It is to benoted that the weights in Table 4 are expressed in grams (g).

TABLE 4 Sample Sample Sample Sample Sample 1 3 4 5 6 (10% Sample (20%(20% (20% (15% Acumer 2 Acumer Acumer Acumer Acumer Component 9932)(Control) 9932) 9932) 9932) 9932) Maltodextrin 79.9 (DE 11.0)Maltodextrin 79.9 (DE 18.0) Maltodextrin 89.8 79.9 84.9 (DE 7.5) gamma-13.7 9.1 13.7 13.7 13.7 13.7 aminopropyl- trihydroxy- silane (1.24%solution) Acumer 20.8 41.7 41.7 41.7 31.2 9932/Cross- linking Agent⁽¹⁾Acrylic 127.8 Binder QRXP 1734⁽²⁾ Water 675.7 663.1 664.8 664.8 664.8670.2 Total (g) 800 800 800 800 800 800 ⁽¹⁾Acumer 9932: a polyacrylicacid resin (46% solids) commercially available from The Dow ChemicalCompany. ⁽²⁾QXRP 1734: a polyacrylic acid resin commercially availablefrom The Dow Chemical Company.

TABLE 5 Sample Sample Sample Sample Sample Sample 1 2 3 4 5 6 TensileStrength 20.7 30.4 20.9 20.6 29.3 26.1 (lbf) LOI (%) 9.7 8.4 9.3 9.511.0 11.3 Tensile/LOI 2.1 3.6 2.3 2.2 2.7 2.3 After Steam aging 18.916.2 19.9 16.2 22.6 26.1 Tensile Strength (lbf) After Steam 9.9 9.5 9.89.4 10.5 11.3 aging LOI (%) After Steam aging 1.9 1.7 2.0 1.7 2.2 2.3Tensile/LOI

From the data set forth in Tables 4 and 5, it was concluded that thebinder formulations demonstrated equal or better tensile strengthscompared to tensile strengths of current commercially availableproducts.

Example 2

The binder formulations set forth in Table 6 were utilized to formhandsheets according to the procedure set forth in Example 1. Thenonwoven fiberglass handsheets were dried and cured for three minutes at400° F. The tensile strength, the loss on ignition (LOI), and thetensile strength divided by the LOI (tensile strength/LOI) for eachsample was determined under ambient and steam conditions. The steamconditions were identical to that set forth in Example 1. In addition,the loss on ignition and tensile strength of each the samples weremeasured according to the procedures described in Example 1. The resultsare set forth in Table 7. It is to be noted that the weights in Table 6are expressed in grams (g).

TABLE 6 Sample 1 Sample 3 Sample 4 10% 20% 20% Citric Acid Sample 2Citric Acid Citric Acid Component 5% SHP Control 5% SHP 5% SHPMaltodextrin 79.9 (DE 11.0) Maltodextrin 79.9 (DE 18.0) Maltodextrin89.8 (DE 7.5) gamma-amino- 13.7 13.7 13.7 13.7 propyltri- hydroxy-silane (1.24% solution) Citric 9.6 19.2 19.2 Acid/Cross- linking AgentAcrylic Binder 191.7 QRXP 1734⁽¹⁾ Sodium 4.8 4.8 4.8 4.8 Hypophosphite(SHP) Water 682.1 589.9 682.5 682.5 Total (g) 800 800 800 800 ⁽¹⁾QXRP1734: a polyacrylic acid resin commercially available from The DowChemical Company.

TABLE 7 Sample 2 Sample 1 Control Sample 3 Sample 4 Tensile Strength(lbf) 16.56 23.31 20.40 20.76 LOI (%) 9.12 7.20 7.99 8.69 Tensile/LOI1.82 3.24 2.55 2.39 After Steam aging 15.67 13.01 13.03 14.86 TensileStrength (lbf) After Steam aging 9.73 7.54 8.78 9.11 LOI (%) After Steamaging 1.61 1.73 1.48 1.63 Tensile/LOI

From the data presented in Tables 6 and 7, it was concluded that binderformulations containing maltodexrin having different DextroseEquivalents (DE) achieved tensile strengths, LOIs, and LOIs after steamaging that were better than or comparable to commercially availableproducts.

Example 3

The binder formulations set forth in Table 8 were utilized to formhandsheets according to the procedure set forth in Example 1. Thenonwoven fiberglass handsheets were dried and cured for three minutes at400° F. The tensile strength, the LOI, and the tensile strength/LOI foreach sample were determined under ambient and steam conditions. Thesteam conditions were identical to that set forth in Example 1. Inaddition, the loss on ignition and tensile strength of each the sampleswere measured according to the procedures described in Example 1. Theresults are set forth in Table 9. It is to be noted that the weights inTable 8 are expressed in grams (g).

TABLE 8 Sample 2 70:30 Sample 5 Sample 1 MD-CA Sample 3 Sample 4 70:3070:30 w/5% SHP 70:30 70:30 MD-CA MD-CA and 10% MD-CA MD-CA w/3% Li-Component w/5% SHP H₃PO₄ w/4% H₃PO₂ w/5% AlCl₃ Carboxylate Maltodextrin45.1 42.6 46.0 45.1 52.0 (DE 11.0) Citric Acid 19.3 14.2 19.2 19.3 23.3gamma- 10.2 11.2 10.3 10.2 11.5 aminopropyl- trihydroxy- silane (1.24%solution) Catalyst 4.1 4.5 (Sodium Hypophosphite) Catalyst 8.5 (85%H3PO4) Catalyst 5.2 (50% H3PO2) Catalyst 6.1 (55.2% AlCl₃) Lithium 4.1Carboxylate (50% conc.) Water (g) 721.3 719.0 719.3 719.3 710.1 **MD =maltodextrin, CA = citric acid, SHP = sodium hypophosphite

TABLE 9 Sample Sample Sample Sample Sample 1 2 3 4 5 Tensile 14.40 11.8711.08 6.54 15.94 Strength (lbf) LOI (%) 6.27 6.28 6.42 5.31 4.87Tensile/LOI 2.30 1.89 1.73 1.23 3.28 After Steam 7.81 5.98 7.84 2.9310.63 aging Tensile Strength (lbf) After Steam 6.95 6.27 6.80 5.44 5.33aging LOI (%) After Steam 1.12 0.95 1.15 0.54 1.99 aging Tensile/LOI

From the data set forth in Tables 8 and 9, it was concluded thatbio-based binder formulations containing different catalysts achievedtensile strengths comparable to that of current commercially availableproducts.

Example 4

The binder formulations set forth in Table 10 were utilized to form R-19fiberglass insulation batts in a manner known by those of skill in theart. The R-19 fiberglass insulation batts had a target 6% LOI and werecured at 510° F. The mechanical properties of the batts at the end ofthe line were determined under ambient conditions. The results are setforth in Table 11.

TABLE 10 Sample 1 Sample 2 Sample 4 90:10 80:20 Sample 3 70:30 MD-CAMD-CA 80:20 MD-CA Component w/5% SHP w/5% SHP MD-PA w/5% SHPMaltodextrin  76 lbs  37 lbs 66 lbs 32 lbs gamma- 0.6 lbs 0.3 lbs 0.6lbs  0.3 lbs  aminopropyl- trihydroxy-silane (24.8% solution) CitricAcid 8.5 lbs  9 lbs — 14 lbs Acrylic Binder — — 36 lbs — (Acumer9932)⁽¹⁾ Sodium 4.2 lbs 2.3 lbs — 2.3 lbs  Hypophosphite Oil Emulsion31.5 lbs   17 lbs 31 lbs 17 lbs (50%) Water 1080.2 lbs   583.4 lbs 1040.4 lbs    586.4 lbs   Total 1201 lbs  649 lbs  1174 lbs  652 lbs ⁽¹⁾Acumer 9932: a polyacrylic acid resin (46% solids) commerciallyavailable from The Dow Chemical Company. **MD = maltodextrin, CA =citric acid, PA = polyacrylic acid, SHP = sodium hypophosphite

TABLE 11 Phenol/Urea/ Sample Sample Sample Sample Formaldehyde 1 2 3 4(Control) Thickness 6.4 6.3 6.3 6.2 6.2 Recovery (in) Stiffness/Sag 2319 35 15 18 (degree)

From the data presented in Tables 10 and 11, it was concluded thatbinder formulations containing maltodextrin with polyacrylic acid ordifferent ratios of maltodextrin and citric acid could be cured undertypical manufacturing conditions and achieved product performancecomparable to that of current commercially available products.

Example 5

The binder formulations set forth in Table 12 were utilized to form R-19fiberglass insulation batts in a conventional manner known by those ofskill in the art. The R-19 fiberglass insulation batts had a target losson ignition (LOI) of 6%. The mechanical properties of the batts weredetermined under ambient conditions. The results are set forth in Table13.

TABLE 12 Sample 1 Sample 2 Sample 3 Sample 4 70:20:10 60:20:20 60:30:1050:30:20 MD-CA-G MD-CA-G MD-CA-G MD-CA-G Component w/5% SHP w/5% SHPw/5% SHP w/5% SHP Maltodextrin 65.8 lbs 56.4 lbs 56.4 lbs 47.0 lbs (50%Solids) Citric Acid 18.8 lbs 18.8 lbs 28.2 lbs 28.2 lbs (50% Solids)Sodium Hypo- 5.66 lbs 5.66 lbs 5.66 lbs 5.66 lbs phosphite (41.5%Solids) Glycerol 4.70 lbs 9.40 lbs 4.70 lbs 9.40 lbs Oil Emulsion 4.24lbs 4.24 lbs 4.24 lbs 4.24 lbs (50% Solids) gamma- 0.37 lbs 0.37 lbs0.37 lbs 0.37 lbs aminopropyl- trihydroxy- silane (24.8% solution) Water545.6 lbs  550.3 lbs  545.6 lbs  550.3 lbs  ** MD = maltodextrin, G =glycerol, CA = citric acid, SHP = sodium hypophosphite

TABLE 13 Sample 1 Sample 2 Sample 3 Sample 4 80:20 70:10:20 60:20:2060:10:30 50:20:30 MDCA MD-G-CA MD-G-CA MD-G-CA MD-G-CA w/5% SHP w/5% SHPw/5% SHP w/5% SHP w/5% SHP Thickness 5.86 6.05 5.82 5.56 5.55 Recovery(in) Stiffness/Sag 40 43 43 33 34 (degree) ** MD = maltodextrin, CA =citric acid, G = glycerol, SHP = sodium hypophosphite

It was concluded from the data set forth in Tables 12 and 13 that binderformulations containing process aid agents (e.g., glycerin) at varyinglevels achieved product performance comparable to that of currentcommercially available products. It was also observed that the uncuredblanket ramp height before entering the oven was improved proportionalto the percent of glycerin present in the binder composition. Forexample, the ramp height increased from 15% to 50% as the percent ofglycerin present in the composition was raised from 5% to 15%.

Example 6

The binder formulations set forth in Tables 14 and 16 were utilized toform handsheets according to the procedure set forth in Example 1. Thenonwoven fiberglass handsheets were dried and cured for three minutes at400° F. The tensile strength, the LOI, and the tensile strength/LOI foreach sample was determined under ambient and steam conditions. The steamconditions were identical to that set forth in Example 1. In addition,the loss on ignition and tensile strength of each the samples weremeasured according to the procedures described in Example 1. The resultsare set forth in Tables 15 and 17. It is to be noted that the weights inTables 15 and 17 are expressed in grams (g).

TABLE 14 Sample 1 Sample 2 Sample 3 Sample 4 80:20 70:20:10 75:20:570:20:10 MD-CA MD-CA-TEOA MD-CA-TEOA MD-CA-DEOA Component w/5% SHP w/5%SHP w/5% SHP w/5% SHP Maltodextrin 116.14 101.62 108.88 101.62 (50%Solids) Citric Acid 14.52 14.52 14.52 14.52 (100% Solids) Sodium 8.758.75 8.75 8.75 Hypophosphite (41.5% Solids) Triethanolamine 7.26 3.63(100% Solids) Diethanolamine 7.26 (100% Solids) gamma- 11.47 11.47 11.4711.47 aminopropyl- trihydroxy-silane (1.24% solution) Water 749.13756.39 752.76 756.39 Total (g) 900 900 900 900 ** MD = maltodextrin, CA= citric acid, TEOA = Triethanolamine, DEOA = Diethanolamine, SHP =sodium hypophosphite

TABLE 15 Sample 1 Sample 2 Sample 3 Sample 4 Tensile 15.7 16.5 15.9 14.6Strength (lbf) LOI (%) 5.74 5.52 5.27 4.79 Tensile/LOI 2.74 3.00 3.033.06

TABLE 16 Sample 7 Sample 8 Sample 6 60:30:10 65:30:5 Sample 9 Sample 1070:30 MD-CA- MD-CA- 60:30:10 65:30:5 MD-CA TEOA TEOA MD-CA- MD-CA-Component w/5% SHP w/5% SHP w/5% SHP TEOA TEOA Maltodextrin 101.62 87.1094.36 91.46 99.08 (50% Solids) Citric Acid 21.78 21.78 21.78 22.86 22.86(100% Solids) Sodium 8.75 8.75 8.75 Hypophosphite (41.5% Solids)Triethanolamine 7.26 3.63 7.62 3.81 (100% Solids) Diethanolamine (100%Solids) gamma- 11.47 11.47 11.47 11.47 11.47 aminopropyl- trihydroxy-silane (1.24% solution) Water 756.39 763.64 760.01 766.58 762.77 Total(g) 900 900 900 900 900 ** MD = maltodextrin, CA = citric acid, TEOA =Triethanolamine, DEOA = Diethanolamine, SHP = sodium hypophosphite

TABLE 17 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10 Tensile 15.5 19.118.9 16.3 18.2 Strength (lbf) LOI (%) 5.20 5.11 4.95 6.00 6.55Tensile/LOI 2.99 3.74 3.83 3.27 2.78

From the data set forth in Tables 14-17, it was concluded that binderformulations containing alkanol amine added as a crosslinking enhancerachieved tensile strengths and LOIs comparable to or better than that ofcurrent commercially available products.

Example 7

The binder formulations set forth in Table 18 and Table 20 were utilizedto form R-21 fiberglass insulation batts in a conventional manner knownby those of skill in the art. The R-21 fiberglass insulation batts had atarget loss on ignition (LOI) of 5.5%. The mechanical properties of thebatts at the end of the line were determined under ambient conditions.The results are set forth in Tables 19 and 20.

TABLE 18 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 80:20 70:30 60:4060:30:10 60:30:5:5 MD-CA MD-CA MD-CA MD-CA-G MD-CA-G-TEOA Component w/5%SHP w/5% SHP w/5% SHP w/5% SHP w/5% SHP Maltodextrin 258.7 lbs  226.4lbs  194.0 lbs  194.0 lbs  194.0 lbs  (68% Solids) Citric Acid 88.0 lbs131.9 lbs  175.9 lbs  131.9 lbs  131.9 lbs  (50% Solids) Sodium 26.5 lbs26.5 lbs 26.5 lbs 26.5 lbs 26.5 lbs Hypophosphite (41.5% Solids)Glycerol 22.0 lbs 11.0 lbs (100% Solids) Triethanolamine 11.0 lbs (100%Solids) Diethanolamine (85% Solids) Oil Emulsion 68.4 lbs 68.4 lbs 68.4lbs 68.4 lbs 68.4 lbs (50% Solids) gamma- 34.6 lbs 34.6 lbs 34.6 lbs34.6 lbs 34.6 lbs aminopropyl- trihydroxy- silane (1.24% solution) Water2228.5 lbs  2218.9 lbs  2209.3 lbs  2227.4 lbs  2227.4 lbs  ** MD =maltodextrin, CA = citric acid, G = glycerol, TEOA = Triethanolamine,DEOA = Diethanolamine, SHP = sodium hypophosphite

TABLE 19 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Stiffness/Sag13.60 9.63 9.65 10.68 11.23 (degree)

TABLE 20 Sample 6 Sample 8 Sample 9 60:30:10 Sample 7 60:30:10 65:30:5Sample 10 MD-CA-TEOA 60:30:10 MD-CA-DEOA MD-CA-DEOA 67:33 Component w/5%SHP MD-CA-TEOA w/5% SHP w/5% SHP MD-CA Maltodextrin 194.0 lbs  203.7lbs  194.0 lbs  210.2 lbs  226.4 lbs (68% Solids) Citric Acid 131.9 lbs 138.5 lbs  131.9 lbs  131.9 lbs  153.9 lbs (50% Solids) Sodium 26.5 lbs26.5 lbs 26.5 lbs Hypophosphite (41.5% Solids) Glycerol (100% Solids)Triethanolamine 22.0 lbs 23.1 lbs (100% Solids) Diethanolamine 25.9 lbs12.9 lbs (85% Solids) Oil Emulsion 68.4 lbs 68.4 lbs 68.4 lbs 68.4 lbs 68.4 lbs (50% Solids) gamma- 34.6 lbs 34.6 lbs 34.6 lbs 34.6 lbs  34.6lbs aminopropyl- trihydroxy-silane (1.24% solution) Water 2227.4 lbs 2234.9 lbs  2224.2 lbs  2221.6 lbs  2224.9 lbs  ** MD = maltodextrin, CA= citric acid, G = glycerol, TEOA = Triethanolamine, DEOA =Diethanolamine, SHP = sodium hypophosphite

TABLE 21 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10 Stiffness/Sag11.85 12.28 9.82 9.85 12.11 (degree)

As shown in Tables 18-21, the addition of glycerol, diethanolamine,and/or triethanolamine to the bio-based binder yielded fiberglassinsulation products having good performance properties, such asacceptable stiffness/sag. In addition, binder formulations containing ablend of maltodextrin and citric acid without the presence of a catalystcured under typical manufacturing conditions and produced acceptablestiffness/sag performance.

Example 8

The binder formulations set forth in Table 22 were utilized to formfiberglass 5 pcf, 1 inch thick ceiling boards in a conventional mannerknown by those of skill in the art. The ceiling boards had a target losson ignition (LOI) of 13%. The mechanical properties of the ceilingboards were determined under ambient conditions. The results are setforth in Table 23. Comparative Samples 1-3 are presented in Table 22 andSample 4, the Control in this experiment, although not specificallyidentified in Table 22, is an Owens Corning 5 pound-per-cubic-foot (pcf)1 inch thick ceiling board, a commercially available product.

TABLE 22 Bio-Based Binder Formulation for 5 pound-per- cubic-foot (pcf),1 inch thick ceiling boards Sample 1 Sample 2 Sample 3 70:30 50:35:1560:30:10 MD-CA MD-CA-G MD-CA-TEOA Component w/5% SHP w/5% SHP w/5% SHPMaltodextrin 709. lbs 506.5 lbs 607.8 lbs (50% Solids) Citric Acid 303.9lbs  354.5 lbs 303.9 lbs (50% Solids) Sodium 61.0 lbs  61.0 lbs  61.0lbs Hypophosphite (41.5% Solids) Glycerol  76.0 lbs (100% Solids)Triethanolamine  50.6 lbs (100% Solids) Surfynol 465  1.1 lbs  1.1 lbs 1.1 lbs (100% Solids) Oil Emulsion 56.4 lbs  56.4 lbs  56.4 lbs (50%Solids) gamma-  4.0 lbs  4.0 lbs  4.0 lbs aminopropyl- trihydroxy-silane (24.8% solution) Water 1384.3 lbs  1447.1 lbs  1426.2 lbs  ** MD= maltodextrin, CA = citric acid, G = glycerol, TEOA = Triethanolamine,SHP = sodium hypophosphite

TABLE 23 Product Performance for 5 pcf, 1 inch thick ceiling boardsSample 1 Sample 2 Sample 3 Sample 4 70:30 50:35:15 60:30:10 Phenol/Urea/MD-CA MD-CA-G MD-CA-TEOA Formaldehyde w/5% SHP w/5% SHP w/5% SHP(Control)⁽¹⁾ Flex Modulus (ksi) 1931 2080 2000 1946 Compressive 37.132.5 37.1 31.1 Load @ 10% Deformation (lbs) ⁽¹⁾Owens Corning 5pound-per-cubic-foot (pcf) 1 inch thick ceiling board, a commerciallyavailable product.

As shown in Tables 22 and 23, the bio-based binder produced ceilingboards having good performance properties, such as improved (orequivalent) flexural modulus and improved compressive load deformation.

Example 9

The binder formulations set forth in Table 24 were utilized to form R-6fiberglass flexible duct media (FDM) in a conventional manner known bythose of skill in the art. The flexible duct media had a target LOI of6%. The mechanical properties of the flexible duct media were determinedunder ambient conditions. The results are set forth in Table 25.

TABLE 24 Bio-Based Binder Formulation for Flexible Duct Media Sample 170:30 MD-CA Component w/5% SHP Maltodextrin (50% Solids) 529.9 lbs Citric Acid (50% Solids) 227. lbs Sodium Hypophosphite 45.6 lbs (41.5%Solids) Red Dye (35% Solids)  9.2 lbs Oil Emulsion (50% Solids) 106.9lbs  gamma-aminopropyl-trihydroxy- 59.6 lbs silane (24.8% solution)Water 3567.2 lbs  ** MD = maltodextrin, CA = citric acid, SHP = sodiumhypophosphite

TABLE 25 Product Performance for R-6 Flexible Duct Media InsulationSample 1 Owens Corning R-6 Phenol/ 70:30 Urea/Formaldehyde FlexibleMD-CA Duct Media Insulation w/5% SHP (Control) Tensile Strength (lbf) 1720

As shown in Tables 24 and 25, the bio-based produced R-6 flexible ductmedia insulation that possessed a tensile strength comparable to that ofan existing R-6 flexible duct media insulation commercial product.

Example 10

The binder formulations set forth in Table 26 were utilized to form R-13fiberglass metal building insulation (MBI) in a conventional mannerknown by those of skill in the art. The ceiling boards had a target LOIof 6.5%. The mechanical properties of the metal building insulation weredetermined under ambient conditions. The results are set forth in Table27.

TABLE 26 Bio-Based Binder Formulation for Metal Building InsulationSample 1 70:30 MD-CA Component w/5% SHP Maltodextrin (50% Solids) 463.9lbs  Citric Acid (50% Solids) 198.8 lbs  Sodium Hypophosphite 39.9 lbs(41.5% Solids) Red Dye (35% Solids)  7.3 lbs Oil Emulsion (50% Solids)84.9 lbs gamma-aminopropyl-trihydroxy- 52.2 lbs silane (24.8% solution)Water 1806 lbs  ** MD = maltodextrin, CA = citric acid, SHP = sodiumhypophosphite

TABLE 27 Product Performance for R-13 Metal Building Insulation Sample 1Owens Corning R-13 Phenol/ 70:30 Urea/Formaldehyde Metal MD-CA BuildingInsulation w/5% SHP (Control) Thickness (in) 4.64 4.66

As shown in Tables 26 and 27, the bio-based binder produced R-13 metalbuilding insulation that had a thickness comparable to that of acommercially available R-13 metal building insulation product.

Example 11

Surface tensions of the bio-based binders containing surfactants tolower the binder surface tension, to improve binder spray atomization,to improve binder distribution uniformity, and to improve binder wettingand moving of the binder to fiber-fiber junctions were compared with aphenol/urea/formaldehyde binder standard. Surface tensions of theinventive bio-based binder compositions were measured using a SurfaceTensionmeter 6000 (manufactured by the SensaDyne Instrument Division ofthe Chem-Dyne Research Group). The instrument was calibrated withdeionized water. Data was recorded every 5 seconds. After the system wasstabilized and the testing had begun, the average value over aone-minute testing period was obtained for each sample. The results areset forth in Table 28.

TABLE 28 Surface tension of the bio-based binder and surfactant addition% on Surface Binder Mixture binder Tension (10% total solids) Surfactantsolids (dyne/cm) phenol/urea/ None None 72.0 formaldehyde (Control)80:20 MD-CA w/5% SHP None None 77.7 80:20 MD-CA w/5% SHP Stanfax⁽¹⁾ 0.146.0 0.3 41.3 0.5 41.9 80:20 MD-CA w/5% SHP Surfynol 465⁽²⁾ 0.1 51.0 0.349.4 0.5 46.2 80:20 MD-CA w/5% SHP Triton ™ 0.1 35.6 GR-PG70⁽³⁾ 0.3 31.30.5 30.1 80:20 MD-CA w/5% SHP Sodium Dodecyl- 0.1 60 Sulfate 0.3 51.90.5 50.8 80:20 MD-CA w/5% SHP Triton ™ 0.1 39.1 CF-10 0.3 39.3 0.5 40⁽¹⁾Stanfax - sodium lauryl sulfate ⁽²⁾Surfynol 465 - ethoxylated2,4,7,9-tetramethyl 5 decyn-4,7-diol ⁽³⁾Triton ™ GR-PG70 -1,4-bis(2-ethylhexyl) sodium sulfosuccinate ⁽⁴⁾Triton ™ CF-10 -poly(oxy-1,2-ethanediyl),alpha-(phenylmethyl)-omega-(1,1,3,3-tetramethylbutyl)phenoxy ** MD =maltodextrin, CA = citric acid, SHP = sodium hypophosphite

It was concluded from observing the results set forth in Table 28 thatthe surface tension of the bio-based binder was reduced by addingsurfactants.

TABLE 29 Coupling agents for the bio-based binderformulations-Fiberglass Handsheets Sample 2 Sample 3 Sample 4 Sample 5Sample 6 70:30 70:30 70:30 70:30 70:30 Sample 1 MD-CA MD-CA MD-CA MD-CAMD-CA 70:30 w/5% SHP w/5% SHP w/5% SHP w/5% SHP w/5% SHP MD-CA and 0.19%and 0.38% and 0.19% and 0.38% and 0.19% w/5% Tyzor ® Tyzor ® Tyzor ®Tyzor ® Tyzor ® Component SHP TE TE AA-75 AA-75 TPT Maltodextrin 90.3 g90.3 g 90.0 g 90.3 g 90.0 g 90.3 g (50% conc.) (DE 11.0) Citric Acid19.4 g 19.4 g 19.3 g 19.4 g 19.3 g 19.4 g gamma- 10.2 g aminopropyl-trihydroxy-silane (1.24% solution) Sodium  3.9 g  3.9 g  3.9 g  3.9 g 3.9 g  3.9 g Hypophosphite (41.5% conc.) Tyzor ® TE 0.16 g 0.32 g (80%Conc.) Tyzor ® AA-75 0.17 g 0.34 g (75% Conc.) Tyzor ® TPT 0.13 g (100%Conc.) Water 676.2 686.3 686.5 686.3 686.5 686.3 Total  800 g  800 g 800 g  800 g  800 g  800 g MD = maltodextrin, CA = citric acid, SHP =sodium hypophosphite

TABLE 30 Mechanical properties for handsheets with the bio-based binderformulations containing different coupling agents Sample 2 Sample 3Sample 4 Sample 5 Sample 6 70:30 70:30 70:30 70:30 70:30 Sample 1 MD-CAMD-CA MD-CA MD-CA MD-CA 70:30 w/5% SHP w/5% SHP w/5% SHP w/5% SHP w/5%SHP MD-CA and 0.19% and 0.38% and 0.19% and 0.38% and 0.19% w/5% Tyzor ®Tyzor ® Tyzor ® Tyzor ® Tyzor ® SHP TE TE AA-75 AA-75 TPT TensileStrength 16.13 16.43 15.79 15.2 15.05 20.17 (lbf) LOI (%) 5.85 6.27 6.346.33 6.17 6.73 Tensile/LOI 2.76 2.62 2.49 2.4 2.44 3.00 After Steam10.66 6.51 6.64 7.30 10.25 10.29 aging Tensile Strength (lbf) AfterSteam 5.03 6.06 6.36 6.58 6.46 8.44 aging LOI (%) After Steam 2.12 1.081.04 1.11 1.59 1.22 aging Tensile/LOI MD = maltodextrin, CA = citricacid, SHP = sodium hypophosphite

From the data set forth in Tables 29 and 30, it was concluded that thebio-based formulations containing different coupling agents achievedtensile strengths comparable to that of current commercially availableproducts.

Example 12

The bio-based binder may emit an aroma depending upon product and curingconditions. To minimize the emission of undesired aromas, variousalkanol amines were added to the binder composition and R-20 productswere produced under typical (conventional) manufacturing conditions. Theproduced materials were cut into 8×8 (inch²), placed in zip bags, andsealed. Ten panelists were provided with a fresh sample bag and thepanelists individually ranked each of the samples from strongest aroma(higher number) to weakest aroma (lower number). The results arepresented in Table 31.

TABLE 31 Aroma decrease in insulation made with the bio-based binderAroma Ranking (intensity Sample Description descending order) Sample 170:30 MD-CA w/5% SHP 4 Sample 2 60:30:10 MD-CA-TEOA 3 Sample 3 65:30:5MD-CA-TEOA 2 w/5% SHP Sample 4 65:30:5 MD-CA-DEOA 1 w/5% SHP ** MD =maltodextrin, CA = citric acid, TEOA = Triethanolamine, DEOA =diethanolamine, SHP = sodium hypophosphite

Based upon the data set forth in Table 31, it was concluded that thearoma generated by the cured insulation product was reduced using aninventive bio-based binder containing an alkanol amine.

Example 13

The binder formulations of Sample 1 and Sample 2 set forth in Table 18combined with the moisture resistant additives listed in Table 32 wereutilized to form fiberglass R-13 insulation products in a conventionalmanner known by those of skill in the art. The R-13 products had atarget LOI of 6.5%. The mechanical properties of the moisture resistanceadditive added bio-binder were determined under ambient conditions. Theresults are set forth in Table 32.

TABLE 32 Additives added to improve water resistance of fiberglassinsulation made with bio-based binder - R-13 batts Amount added Stiff-Additive (% on Binder ness/Sag Description added Solids) (degree) 80:20MD-CA w/5% SHP 39 70:30 MD-CA w/5% SHP 28 70:30 MD-CA w/5% SHP PolonMF56 0.3 32 70:30 MD-CA w/5% SHP SVE-148 0.3 30 70:30 MD-CA w/5% SHPLE-743 0.3 31 70:30 MD-CA w/5% SHP Silres BS-1042 0.3 37 70:30 MD-CAw/5% SHP ICM-2153 0.3 35 70:30 MD-CA w/5% SHP Silquest 0.3 40 Y-9669 **MD = maltodextrin, CA = citric acid, SHP = sodium hypophosphite

Based upon the data set forth in Table 32, it was concluded that thebio-based binder formulations containing different moisture resistantadditives obtained a fiber glass insulation product with performancecapabilities comparable to that of commercially available fiber glassinsulation products.

Example 14

An environmental emission test was using the basic formulation set forthas Sample 1 of Table 18 together with either alone or with an existingemulsified mineral de-dusting oil. The test was conducted over a periodof at least 5 hours using a conventional production line to make an R-19insulation product for each formulation including a control. A typicalemission sampling analytical procedure was followed and the filteredparticulate emission and formaldehyde emission were listed in the Table33.

TABLE 33 Forming Emission Test Results Binder Type Binder Type BinderType Phenol/ Compound/Sample MDCA MDCA-Veg. Urea/Formaldehyde Trainlbs/hour Oil lbs/hour (Control) lbs/hour Filtered Particulate, 5.4995.064 6.737 M5/202 Formaldehyde M316 0.028 0.023 0.414

From the data set forth in Table 33, it was concluded that the bio-basedbinder, when applied in a conventional fiber glass insulationmanufacturing process, reduced forming particulate emission by 18% ormore and nearly eliminated formaldehyde emission during the formation ofthe insulation. It is noted that the small amount of formaldehydedetected might have been derived from formaldehyde binder residue orsome other contamination.

The invention of this application has been described above bothgenerically and with regard to specific embodiments. Although theinvention has been set forth in what is believed to be the preferredembodiments, a wide variety of alternatives known to those of skill inthe art can be selected within the generic disclosure. The invention isnot otherwise limited, except for the recitation of the claims set forthbelow.

1-26. (canceled)
 27. A fibrous product comprising: a plurality ofrandomly oriented glass fibers; and a formaldehyde-free, thermosetting,bio-based binder composition applied to at least a portion of saidfibers, said binder composition comprising the reaction product of: atleast one carbohydrate having reactive hydroxyl groups; and at least onecrosslinking agent having reactive carboxylic acid groups.
 28. Thefibrous product of claim 27, wherein said product is a flexible,low-density product having a density of from about 0.3 to about 4 pcf.29. The fibrous product of claim 28, wherein said binder composition ispresent in an amount from about 2% to about 13%.
 30. The fibrous productof claim 27, wherein said product is a rigid product having a density offrom about 1.5 to about 10 pcf.
 31. The fibrous product of claim 30,wherein said binder composition is present in an amount from about 2% toabout 20%.
 32. The fibrous product of claim 27, wherein said product hasa density of from about 3 to about 8 pcf.
 33. The fibrous product ofclaim 32, wherein said binder composition is present in an amount fromabout 3% to about 15%.
 34. The fibrous product of claim 27, wherein saidproduct is a rigid product having a density of from about 1.5 to about10 pcf, and is shaped cylindrically to fit around a section of pipe. 35.The fibrous product of claim 27, wherein said product is made by arotary fiberization process.
 36. The fibrous product of claim 27,wherein said product is a non-woven product made by an air-laid process,said product having a density of from about 0.8 to about 4 pcf.
 37. Thefibrous product of claim 36, wherein said binder composition is presentin an amount from about 5% to about 20%.
 38. The fibrous product ofclaim 27 wherein said at least one carbohydrate is a carbohydrate havinga dextrose equivalent number from 2 to
 20. 39. The fibrous product ofclaim 38, wherein said at least one carbohydrate is a water-solublepolysaccharide selected from the group consisting of pectin, dextrin,maltodextrin, starch, modified starch, starch derivatives andcombinations thereof.
 40. The fibrous product of claim 27, wherein saidbinder composition in a cured state comprises at least one polyester.41. The fibrous product of claim 40, wherein said crosslinking agent isselected from the group consisting of polycarboxylic acids, salts ofpolycarboxylic acid, anhydrides, monomeric carboxylic acid withanhydride, polycarboxylic acid with anhydride, citric acid, salts ofcitric acid, adipic acid, salts of adipic acid, polyacrylic acid, saltsof polyacrylic acid, polyacrylic acid based resins and combinationsthereof.
 42. The fibrous product of claim 27, wherein said product isfree of added formaldehyde.
 43. The fibrous product of claim 27, whereinsaid fibrous product is an insulation product.
 44. The fibrous productof claim 27, wherein said fibrous product is a non-woven fibrous matproduct having a first major surface and a second major surface; andhaving the binder composition at least partially coating the first majorsurface.
 45. The non-woven mat of claim 44, wherein said bindercomposition in a cured state comprises at least one polyester.